DE2823303A1 - PROCESS FOR THE PRODUCTION OF 1.2-POLYBUTADIENE WITH ADJUSTED MOLECULAR WEIGHT - Google Patents

Description

The invention relates to a method for adjusting the molecular weight of 1,2-polybutadienes.

The physical and mechanical properties as well as the processability of rubbery or rubbery as well as resinous polymers depend strongly on the respective molecular weights. It is therefore It is desirable to be able to produce polymers with an optimal molecular weight for the particular application.

Adjustment of the molecular weight of 1,2-polybutadiene has so far been carried out by setting the catalyst concentration and the process conditions accordingly in the preparation of the catalyst, the monomer concentration, the polymerization temperature or the like. or by addition of substances that regulate molecular weight.

However, these methods of adjusting the molecular weight of 1,2-polybutadienes are common to most

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_ ¹ Y _M

Cases in terms of product properties _s productivity j cost, the production facility to be used and the like are not necessarily advantageous. In particular, these processes lead in numerous cases to a reduction in the polymerization activity and to a change in the microstructure or the degree of crystallinity of the 1,2-polybutadiene.

As a result of extensive experimental investigations to develop a method for the advantageous Production of 1,2-polybutadiene with arbitrarily adjustable molecular weight was according to the invention found that 1,2-polybutadienes with discontinued Molecular weight without any change in microstructure and degree of crystallinity as well can be produced practically without deterioration in the polymerization activity if 1,3-butadiene with one of (A) a cobalt compound, (B) an organic phosphine compound, (C) an aluminum trialkyl and (D) a catalyst consisting of water in the presence of (E) at least one of the allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides and tertiary aliphatic halides selected compound is polymerized.

The invention is accordingly based on the object of a process for the production of 1,2-polybutadiene to be specified with a molecular weight that can be set as desired. The procedure is intended to stop the Molecular weight of 1,2-polybutadiene without deterioration the polymerization activity or change in

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Microstructure or crystallinity of the product.

The invention provides a process for the preparation of 1,2-polybutadiene with adjusted molecular weight on, which is characterized in that 1,3-butadiene with a catalyst

(A) a cobalt compound,

(B) an organic phosphine compound,

(C) an aluminum trialkyl and

(D) water in an amount of 0.25 to 1.5 moles per mole of aluminum trialkyl

in the presence of

(E) at least one of the alkyl halides, alkyl-substituted alkyl halides, benzyl halides, alkyl-substituted benzyl halides and tertiary aliphatic halides selected compound

is polymerized.

In the process according to the invention, in which the polymerization of 1,3-butadiene with the above polymerized catalyst consisting of four components C (A) to (D)) in the presence of said component (E) the molecular weight of the resulting 1,2-polybutadienes can be adjusted by adjusting the amount of the component (E) without reducing the 1.2 content and the degree of crystallinity of the resulting 1.2-polybutadiene can be adjusted to any desired values while maintaining the high polymerization activity.

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The cobalt compound used as component (A) of the catalyst used according to the invention can among a multitude of cobalt compounds with an apparent valence from zero to the highest valency to be selected; preferred examples of such cobalt compounds are cobalt halides, cobalt sulfates, Cobalt nitrates, cobalt carbonates, cobalt phosphates, cobalt hydroxides, cobalt cyanates, cobalt thiocyanates, Cobalt naphthenates, cobalt octenoates and complexes with carbonyl, isonitrile, vinyl compounds, cyclopentadienyl, iC-allyl or its derivatives, acetylacetone, acetoacetic acid and the like as ligands. Individual examples of such compounds are about the cobalt (II) bromide-triphenylphosphine complex, Cobalt (II) acetylacetonate, cobalt octenoate, Cobalt naphthenate, cobalt (II) chloride, cobalt (II) bromide, Cobalt (II) iodide and complexes of these cobalt halides with pyridine, cobalt ethyl xanthate, cobalt isopropyl xanthate, cobalt butyl xanthate, cobalt phenyl xanthate etc.

Complexes of the cobalt compounds with the phosphine compounds (component (B)) can also be used will. Among these cobalt compounds which can be used according to the invention are cobalt (II) acetylacetonate, cobalt naphthenate, Cobalt (II) chloride and cobalt (II) bromide as well Complexes of these cobalt compounds with phosphine compounds are most preferred.

Component (B) is a phosphine compound of the general formula P (R) · ,, where R represents an alkyl or aryl group; , examples of such phosphine compounds include, for example triethylphosphine _f triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tri-m-phenylpheny! phosphine, tri-m-xylylphosphin,

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Tri-m-tolylphosphine and the like.

It should also be noted that component (B) does not have to be added if a Complex with an organic phosphine compound as a ligand such as a bis (triphenylphosphine) complex of cobalt chloride or cobalt bromidej a bis (tri-m-xylylphosphine) complex of cobalt chloride or cobalt bromide or a bis (tri-m-tolylphosphine) complex of cobalt chloride or bromide is used as the cobalt compound of component (A).

The organoaluminum compound used according to the invention as component (C) is included among the compounds of general formula AlR., in which R is an alkyl group represents. The alkyl group can be either straight-chain or branched, with alkyl groups with 1 to 6 carbon atoms are preferred. Preferred examples of such organoaluminum compounds are trimethylaluminum, Triethyl aluminum, triisobutyl aluminum, trihexyl aluminum and the like.

Examples of component (E) include the following compounds:

(a) Allyl halides and alkyl substituted allyl halides such as allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, l-bromo-2-butene, l-chloro-2-butene, l-bromo-2-methyl-2-propene and the like, among which allyl chloride and allyl bromide are most preferred;

(b) Benzyl halides and alkyl-substituted benzyl halides such as benzyl chloride, benzyl bromide, Benzyl iodide, p-methylbenzyl chloride, p-methyl-

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- li -

benzyl bromide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-t-butylbenzyl chloride and the like, among which benzyl chloride, benzyl bromide and p-methylbenzyl chloride are most preferred,

as

(c) tertiary aliphatic halides such as t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, 2-bromo-2-methylbutane, 2-chloro-2-methylpentane, 2-chloro-2-methylhexane and the like, among which t-butyl chloride and t-butyl bromide are preferred are.

These compounds (E) can be used in combination of two or more. The compounds (E) can also be used as such ⁱⁿ a form diluted with a solvent or monomer.

The amount of the compound (E) used in the process according to the invention is in the range from 0.01 to 10 moles, preferably 0.05 to 5 moles, and more preferably 0.1 to 3 moles per mole of the catalyst component (C).

The use of more than 10 moles of the compound (E) leads to a deterioration in the polymerization activity, while the use of less than 0.01 Mole of this compound does not give a satisfactory molecular weight regulating effect.

The molar ratio of the cobalt compound to the organoaluminum compound is usually 1/1 to 1/1000, and preferably 1/5 to 1/100; however, as the vinyl content as well as the degree of crystallinity of the obtained poly-

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meren are not strongly influenced by this ratio, the mixing ratios of the relevant Components depending on the polymerization activity and the desired molecular weight of the product in be chosen appropriately.

The amount of water used as component (D) in the process according to the invention is narrower Relation to the amount of organoaluminum compound added. It is important that the water in a Amount of 0.25 to 1.5 moles per mole of the organoaluminum compound is used. When the amount of water is below The polymerization activity becomes 0.25 mol or over 1.5 mol per mol of the organoaluminum compound of the catalyst is greatly reduced. The preferred amount of water is 0.5 to 1.0 moles per mole of the Organoaluminum compound. Here and below, the amount of water is the total amount of water as a whole Understood polymerization system present water.

The organic phosphine compound, ie the component (B) of the catalyst, is used in an amount of at least 0.2 moles and usually 0.2 to 50 moles, preferably 1 to 10 moles, per mole of the cobalt compound used.

Polybutadienes with 1Λ configuration are obtained in larger amounts when the amount of the organic phosphine compound added is below 0.2 mol.

On the other hand, when the amount of the organic phosphine compound added is too much, the polymerization activity becomes of the catalyst deteriorated.

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The polymerization reaction according to the invention can be carried out either continuously or batchwise Combining 1,3-butadiene with the above Catalyst can be carried out in a solvent. The one used in the polymerization reaction The amount of catalyst is usually from about 0.001 to 1 mmol, and preferably from 0.01 to 0.5 mmol, based on on the cobalt compound, per mole of butadiene.

When carrying out the process according to the invention, the following orders of addition are the relevant Recommended components:

(a) addition of solvent, water (D), 1,3-butadiene, Aluminum trialkyl (C), molecular weight regulating substance (E) and the cobalt compound

(A) in the order given;

(b) addition of solvent, 1,3-butadiene, (E), (C), (D) and (A) in the order given;

(c) Adding the previously mixed and stirred components (C) and (E) to a mixture of solvent, 1,3-butadiene and (D) and then Addition of (A);

(d) adding a previously prepared and stirred mixture of (E) and part of (C) together with the remaining amount of (C) to a mixture of solvent, 1,3-butadiene and (D) and subsequent addition of (A).

The use of a stirred mixture of some or all of the aluminum trialkyl (C) and the molecular weight regulating substance (E) can

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according to the invention to a stronger regulatory effect on the molecular weight without worsening the Result in polymerization activity than when a non-agitated mixture is used. the end for this reason, the order of addition (c) or (d) given above is preferred.

The solvent used for the polymerization in the present invention may be a hydrocarbon or a halogenated one Be hydrocarbon. Examples of such hydrocarbon solvents which can be used in the present invention include benzene, toluene, n-pentane, n-hexane, cyclohexane, and the like; Examples of halogenated hydrocarbon solvents are about methylene chloride, chloroform, chlorobenzene and the like.

The use of halogenated hydrocarbons as solvents is preferred according to the invention, among them most methylene chloride.

The polymerization reaction according to the invention can be carried out at a temperature of from -40 to 100 ^° C. and preferably from -20 to 80 ^° C. under a pressure which is sufficient to keep the reaction mixture essentially in the liquid phase.

The 1,2-polybutadienes obtainable according to the invention are in an extremely wide range of applications, both alone and in combination with other materials such as rubber, caoutchouc or synthetic resins can be used. Typical and recommended uses for such polymers are for example the production of films or foils, various types of pipes and hoses, hot melt adhesives, different types of shaped bodies like

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such as footwear and the like and photosensitive resin materials etc.

The invention is explained in more detail below with reference to exemplary embodiments; the details are only exemplary.

In the examples and comparative examples, the Staudinger index IV] of the polymers was ^{calculated from the viscosity measured in toluene at 30 °} C. The microstructure of the polymers was determined from the IR absorption spectra. The degree of crystallinity was determined by the density gradient method in the tube by setting the density of 1.2-polybutadiene with a degree of crystallinity of 0 % at 0.892 g / ml and the density of 1.2-polybutadiene with a degree of crystallinity of 100% at 0.963 g / ml.

example 1

In a 100 ml pressure bottle, 28 ml of methylene chloride, 0.125 mmol of water (using methylene chloride with a water content of 900 ppm), 6 g of 1,3-butadiene, 0.25 mmol of triisobutylaluminum, a predetermined amount of a 0.05 M solution of was polymerized h at 10 ⁰ C and the mixture 1 presented allyl bromide, allyl chloride, allyl iodide or benzyl chloride in methylene chloride and 0.005 mmol of cobalt bis (triphenylphosphine) dibromide in the order listed. After the polymerization, methanol, which contained a small amount of 2,6-di-t-butyl-p-cresol, was added to the solution to stop the polymerization reaction; for coagulation and precipitation of the polymer, the reaction

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mixture then poured into a large amount of a methanol-hydrochloric acid solution and then dried overnight at hO ⁰ C in a vacuum.

The results obtained are shown in Table 1.

Comparative example 1

The procedure was as in Example 1, with the difference that no halide was used as a molecular weight regulator Substance was used.

The results obtained are shown in Table 1 .

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Table 1

co
ο
co
co
cn

I.
Ver Molecular weight regulation
producing substance mmol yield Kl (30 ⁰ C,
Toluene) I.
! 1.2 salary Crystalline
degree of efficiency No. Art T "■""
; 0.05 "(*) (dl / g) CO (%) : 1 Allyl bromide 94 1.10 94 25.5 I. 2 ti 85 0.68 95 26.5 i j Il 80 0.60 95 26.4 I. 4th Allyl chloride 87 0.79 95 26.1; 5 Il 82 0.68 95 26.4 6th Allyl iodide 89 0.93 95 25.8 j 7th Il ο, ι 79 0.71 95 26.2 8th Benzyl chloride 0.25 82 0.85
! 2.38 95 26.0 Ver _T
same
example
1 ' without ο, ι 98 I ⁹³ 24.0 0.25 0.1 0.25 0.1
ί 0

OO CD CO

Example 2

72 g of methylene chloride, 0.048 mmol of water, 6.0 g of 1,3-butadiene, 0.12 mmol of triisobutylaluminum, 0.036 mmol of benzyl chloride and 0.008 mmol of cobalt bis (tri-m-xylylphosphine) dibromide were placed in a 100 ml pressure bottle in the presented sequence, after which the mixture was ^{polymerized for 1 h at 5 0} C (experiment no. 9)

A similar polymerization was carried out under the same reaction conditions as above, with the difference that a ^{mixture of triisobutylaluminum and benzyl chloride prepared beforehand and stirred at 40 °} C. for 1 hour was used (experiment no. 10).

After the polymerization reaction, the reaction mixture was further treated in the same manner as in Example 1 .

The results obtained are shown in Table 2 .

Comparative example 2

The procedure was as in Example 2, with the difference that there was no molecular weight regulating substance was used.

The results obtained are shown in Table 2.

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Table 2

oo ο co

αο

Molecular weight regulators substance

Art

Benzyl chloride

Comparative example

. 2 I.

L.: I

without

stir

without stirring

with stirring

yield

85
87

83

Kl ⁽³ °

Toluene)

(dl / g) 1.74 1.26

2.27

! 1.2 Ge
' stop

95

95

Krxstallinx- j degree of efficiency:

34.2 34.6

34.4

Example 3

In a 100 ml pressure bottle, 72 g of methylene chloride, 0.048 mmol of water, 6.0 g of 1,3-butadiene and a previously prepared solution by mixing 0.12 mmol of triisobutylaluminum and a predetermined amount of a molecular weight regulating substance and stirring the resulting solution for 1 hour were added HO C prepared mixture presented in the order given, whereupon 0.008 mmol of cobalt bis (tri-m-xylylphosphine) dibromide were added. The resulting mixture was ^{polymerized at 5 °} C. for 1 h. After the polymerization reaction, the reaction mixture was treated as in Example 1.

The results obtained are shown in Table 3.

Comparative example 3

The procedure was as in Example 3, with the difference that no molecular weight regulating substance was used became.

The results obtained are shown in Table 3.

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Table 3

ϊ No. Molecular weight regulation
producing substance mmol yield
[Oil ^ O ⁰ C,
Toluene ) 1.2-Ge
stop Crystalline
wheel of fortune ί ¹³ Art 0.015 (*) (dl / g) (*) (%) I. ^; 12th Benzyl chloride 0.03 85 1.70 95 34.4 : i3 11 0.045 92 1.52 95 34.2 14th Il 0.06 86 1.31 95 34.9 15th dd 0.015 82 1.18 95 34.3 16 t-butyl bromide 0.03 87 1.65 95 34.2 17th It 0.045 91 1.48 94 34 ₅ 1 18th Il 0.06 80 1.12 95 34.8 ■ 19 ! I 0.015 80 1.01 95 33.9 '20 Allyl bromide 0.03 88 1 * 57 95 34.3 : 21 It 0.045 87 1 »53 95 34.2 22nd ti 0.06 88 1.39 94 33.8 It 90 1.25 95 34.1

ro co oo

Table 3

(Continuation)

CX!

CjD CO cn

23 ι
Benzyl bromide; 0.015 85 1.57 94 34.3 24 It * 0.03 86 1.44 95 34.0 25th it ^: 0.045 80 1.21 95 33.7 26th Il 0.06 79 1 ·, 15 95 34.2 Comparison
example
3 without - 85 2.27 94 34.4

ro ro

ro co co

co

Example 4

The procedure was as in Example 3, with the difference that one of the organoaluminum compounds given in Table 4 was used with an equimolar amount of a molecular weight regulating substance as in Example 4 at various Temperatures was mixed and stirred, whereupon the mixture thus stirred together with the remaining amount of the organoaluminum compound was added to the reaction system.

The results obtained are shown in Table 4.

Comparative Examples 4 and 5

The procedure was as in Experiment No. 27 or 33 in Example 4, with the difference that there were no molecular weight regulators Substance was used.

The results obtained are shown in Table 4.

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Table 4

CD ',
CO

attempt

No.

27

28 29

30th

51 32

Organoaluminum compound

Art

Triisobutyl aluminum

Al «

molecular | weight regulating de Subst at z

• ι

I stirring

Art

i mmol

( ⁰ C)

yield

t-butyl-; o, O36 chloride

Allylic chloride

Benzyl chloride

, - triethylalu- ■ minium

40

65 40

40 65 90 40

jrfl (30 ⁰ CJ 1.2-Ge

Toluene) ^content (dl / g) ι

86 85 90

85 75 75 85

1.62 1.53 1.71

1.18 1.10 1.15 1.80

94 94 95

95 95 95 93

[Crystal! - degree of j nity ·;

34.3 34.1 34.4

34.0 34.4

34.3 34.0

Comp. JTriisobutyl Ex. 4 aluminum

" ₅ J triethyl

kluminium

85

87

2.25

2.52

94

93

34.4

34.5

ro oo co

Annotation; With Al 'that amount of the organoaluminum compound (mmol) is abbreviated, the previously mixed with the molecular weight regulating substance and stirred (the total amount of the organoaluminum compound used was 0.12 mole).

Example 5

The procedure was as in Experiment No. 27 in Example U, with the difference that 0.12 mmol of triisobutylaluminum was used as the aluminum trialkyl compound, the amount of molecular weight regulating substance was varied and part of the triisobutylaluminum was previously mixed with the molecular weight regulating substance in a molar ratio of 1: 1 was mixed and ^{stirred at 40 0} C for 1 h.

The results obtained are shown in Table 5 .

Comparative Examples 6 to 8

The procedure was as in Experiment No. 35 in Example 5 with the difference that the t-butyl chloride by n-butyl chloride (comparative example 6) or s-butyl chloride (Comparative Example 7) was replaced or no molecular weight regulating substance was used (Comparative Example 8th).

The results obtained are shown in Table 5 .

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ORIGINAL INSPECTED

Table 5

co ο CD co cn

ο -j

cn

attempt
No. Molecular weight regulation
producing substance mmol yield
(?) pa (30 ° c,
Toluene)
(dl / g) 1.2-Ge
stop
(5) Crystalline
degree of efficiency
(3) ! 3 " Art 0.012 86 1.99 94 34.3 • 35 t-butyl chloride 0.024 88 1.75 95 34.0 ; 36 Il 0.036 83 1.62 94 34.4 Comp.-
Example 6 Il 0.024 84 2.24 94 33.9 7th n-butyl chloride 0.024 j 88 2.24 94 34.1 " 8th s-butyl chloride ^: 85 2.27 94 34.4 without

ro

ro

OO

OO

OO CD

Comparative Examples 9 to 11

The procedure was the same as in Experiment No. 9 in Example 2, with the difference that instead of of the benzyl chloride, an inorganic halide according to Table 6 was used.

The results obtained are shown in Table 6 .

Table 6

inorganic

SSgSfSr.

10
11

Kind of amount

(mmol)

O, - - -ι SiCl ₃ O, 012 j PCl ₃ O, 012 TiCl ₃ 012

{Toluene) (dl / g)

2.32

Example 6

The tests were carried out in the same manner as in Example 2 except that as the cobalt compound Bis- (tri-m-tolylphosphine) dichloride and as molecular weight regulating substance p-methylbenzyl chloride was used.

The results obtained are shown in Table 7.

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Comparative example 12

The procedure was as in Example 6, with the difference that there was no molecular weight regulating substance was used.

The results obtained are shown in Table 7 .

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Table 7

co ο co co cn

“J

O .0

attempt
No. Molecular weight sre-
regulating substance stir yield
(50 Kl (30 ⁰ C,
toluene
(dl / g) 1.2-Ge
stop
CO Crystalline
degree of nature
(OK 37
38 Art without
stir
stir 87
90 1.30
1.02 95
95 31.2
31.1 Comp.-
example
12th p-methylbenzyl
chloride
Il 89 1.95 95 31.1 without

s-

OO

"IJ

Γ; ι

rrf D

GO GO O

Example 7

according to example 2

The procedure was as in Experiment 9 with the difference that cobalt bis (triethylphosphine) dibromide and a mixture of 0.018 mmol of benzyl bromide and 0.018 mmol p-methylbenzyl chloride were used.

The results obtained are shown in Table 8.

Comparative example

The procedure was as in Example 7 with the difference that neither benzyl bromide nor p-methylbenzyl chloride were used.

The results obtained are shown in Table 8 .

Tabel

attempt
No.

molecular

weight loss

regulating

jbenzyl bromide,

p-methylbenzyl chloride

Compare example
13th

yield

89

[n] (30 ° c,
Toluene)
(dl / g) 1.2 salary
(?) Crystalline
degree of nature
(5S) 1.05 94
95 0 1.95 0

803 8 51/0716

In summary, the invention relates to a process for the preparation of 1,2-polybutadiene by polymerization of 1,3-butadiene with a catalyst made from (A) a cobalt compound, (B) an organic phosphine compound, (C) an aluminum trialkyl and (D) water in an amount of 0.25 to 1.5 moles per mole of the aluminum trialkyl compound, where by adding (E) at least one of the allyl halides, the alkyl-substituted Ally! Halides, the benzyl halides, the alkyl-substituted ones Benzyl halides and the tertiary aliphatic halides to the reaction system Adjustment of the molecular weight of the respective 1,2-polybutadiene is made possible to a desired value without a change in the microstructure and in the Degree of crystallinity of the product is caused or a Deterioration of the polymerization activity occurs.

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Claims (29)

Expectations Ij Process for the preparation of 1,2-polybutadienes with adjusted molecular weight ,. characterized in that 1,3-butadiene with a catalyst (A) a cobalt compound, (B) an organic phosphine compound, (C) an aluminum trialkyl and (D) water in an amount of 0.25 to 1.5 moles per mole of aluminum trialkyl in the presence of (E) at least one of the alkyl halides, alkyl-substituted alkyl halides, benzyl halides, alkyl-substituted benzyl halides and tertiary aliphatic halides selected compound is polymerized. 2. The method according to claim 1, characterized in that component (E) in an amount of 0.01 to 10 moles per mole of component (C) is used. 3. The method according to claim 1, characterized in that component (E) in an amount of 0.1 to 3 moles per mole of component (C) is used. 8l- (A3O27-O3) -SP-Bk 809851/0716 Original 4. The method according to claim 1, characterized in that the catalytic polymerization at a temperature from -40 to 100 C. 5. The method according to any one of claims 1 to 4, characterized in that as component (A) cobalt chloride, Cobalt bromide, cobalt iodide, cobalt naphthenate, cobalt octenoate, Cobalt trisacetylacetonate, cobalt bisacetylacetonate or cobalt carbonyl is used. 6. The method according to any one of claims 1 to 4, characterized in that as component (B) triethylphosphine, Triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tri-m-phenylphenylphosphine, tri-m-xylylphosphine or tri-m-tolylphosphine is used. 7. The method according to any one of claims 1 to 4, characterized in that the components (A) and (B) in the form of a complex can be used with one another. 8. The method according to claim 7, characterized in that the complex of bis (triphenylphosphine) complex of cobalt chloride or cobalt bromide, the bis (tri-m-xylylphosphine) complex of cobalt chloride or cobalt bromide, or the bis (tri-m-tolylphosphine) complex of cobalt chloride or cobalt bromide is used. 9. The method according to any one of claims 1 to 4, characterized in that that as component (C) trimethyl aluminum, triethyl aluminum, trixsobutyl aluminum or trihexyl aluminum is used. 10. The method according to any one of claims 1 to 4, characterized in, that component (E) is selected from allyl halides and alkyl-substituted allyl halides will. Ö09851 / 0716 11. The method according to claim 10, characterized in that that component (E) is selected from allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, l-bromo-2-butene, l-chloro-2-butene and l-bromo-2-methyl-2-propene is selected. 12. The method according to claim 10, characterized in that as component (E) allyl chloride or allyl bromide is used. 13. The method according to any one of claims 1 to 4, characterized characterized in that component (E) is selected from the benzyl halides and the alkyl-substituted ones Benzyl halides is selected. 14. The method according to claim 13, characterized in that component (E) is selected from benzyl chloride, benzyl bromide, Benzyl iodide, p-methylbenzyl chloride, p-methylbenzyl bromide / O-methylbenzyl chloride, m-methylbenzyl chloride and p-t-butylbenzyl chloride is selected. 15. The method according to claim 13, characterized in that that benzyl chloride, benzyl bromide or p-methylbenzyl chloride is used as component (E). 16. The method according to any one of claims 1 to 4, characterized characterized in that a tertiary aliphatic halide is selected as component (E). 17. The method according to claim l6, characterized in that component (E) is selected from t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, 2-bromo-2-methylbutane, 2-chloro-2-methylpentane and 2-chloro-2-methylhexane are selected will. 809851/0716 18. The method according to claim 16, characterized in that that as component (E) t-butyl chloride or t-butyl bromide is used. 19 · Method according to one of claims 1 to 4, characterized characterized in that the polymerization of 1,3-butadiene with the catalyst in the presence of component (E) in a solvent is made. 20. The method according to claim 19, characterized in that a hydrocarbon or a solvent is used
halogenated hydrocarbon is used. 21. The method according to claim 19, characterized in that the solvent benzene, toluene, n-pentane, n-hexane or cyclohexane is used. 22. The method according to claim 19, characterized in that the solvent is methylene chloride, chloroform or Chlorobenzene is used. 23. The method according to claim 19, characterized in that methylene chloride is used as the solvent. 24. The method according to claim 19, characterized in that component (D), butadiene, component (C),
the component (E) and the component (A) are added to the solvent in the order given. 25. The method according to claim 19 , characterized in that 1,3-butadiene, component (E), component (C), component (D) and component (A) are added to the solvent in the order given. 809851/0716 26. The method according to claim 19 j, characterized in that that a stirred mixture of component (C) and component (E) to a mixture of the solvent, 1.3 ~ Butadiene and component (D) are added and then component (A) is added. 27. The method according to claim 19, characterized in that a stirred mixture of component (E) and one Part of component (C) is added to a mixture of the solvent, 1,3-butadiene and component (D) and then the remaining amount of component (C) is added. 28. The method according to claim 1, characterized in that the organic phosphine compound in an amount from 0.2 to 50 moles per mole of the cobalt compound is used will. 29. The method according to claim 1, characterized in that the catalyst in an amount of 0.001 to 1 mmol is used based on the cobalt compound per mole of 1,3-butadiene. 8098 5 1/0716